Carbonate formation in salt dome cap rocks by microbial anaerobic oxidation of methane.

Major hydrocarbon accumulations occur in traps associated with salt domes. Whereas some of these hydrocarbons remain to be extracted for economic use, significant amounts have degraded in the subsurface, yielding mineral precipitates as byproducts. Salt domes of the Gulf of Mexico Basin typically exhibit extensive deposits of carbonate that form as cap rock atop salt structures. Despite previous efforts to model cap rock formation, the details of subsurface reactions (including the role of microorganisms) remain largely unknown. Here we show that cap rock mineral precipitation occurred via closed-system sulfate reduction, as indicated by new sulfur isotope data. 13C-depleted carbonate carbon isotope compositions and low clumped isotope-derived carbonate formation temperatures indicate that microbial, sulfate-dependent, anaerobic oxidation of methane (AOM) contributed to carbonate formation. These findings suggest that AOM serves as an unrecognized methane sink that reduces methane emissions in salt dome settings perhaps associated with an extensive, deep subsurface biosphere.

Preservation of overmature, ancient, sedimentary organic matter in carbonate concretions during outcrop weathering.

Concretions are preferentially cemented zones within sediments and sedimentary rocks. Cementation can result from relatively early diagenetic processes that include degradation of sedimentary organic compounds or methane as indicated by significantly 13 C-depleted or enriched carbon isotope compositions. As minerals fill pore space, reduced permeability may promote preservation of sediment components from degradation during subsequent diagenesis, burial heating and outcrop weathering. Discrete and macroscopic organic remains, macro and microfossils, magnetic grains, and sedimentary structures can be preferentially preserved within concretions. Here, Cretaceous carbonate concretions of the Holz Shale are shown to contain relatively high carbonate-free total organic carbon (TOC) contents (up to ~18.5 wt%) compared to the surrounding host rock (with <2.1 wt%). TOC increases with total inorganic carbon (TIC) content, a metric of the degree of cementation. Pyrite contents within concretions generally correlate with organic carbon contents. Concretion carbonate carbon isotope compositions (δ13 Ccarb ) range from -22.5 to -3.4‰ (VPDB) and do not correlate strongly with TOC. Organic carbon isotope compositions (δ13 Corg ) of concretions and host rock are similar. Thermal maturity data indicate that both host and concretion organic matter are overmature and have evolved beyond the oil window maturity stage. Although the organic matter in general has experienced significant oxidative weathering, concretion interiors exhibit lower oxygen indices relative to the host. These results suggest that carbonate concretions can preferentially preserve overmature, ancient, sedimentary organic matter during outcrop weathering, despite evidence for organic matter degradation genetic mechanisms. As a result, concretions may provide an optimal proxy target for characterization of more primary organic carbon concentrations and chemical compositions. In addition, these findings indicate that concretions can promote delayed oxidative weathering of organic carbon in outcrop and therefore impact local chemical cycling.

Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures.

Methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ∼0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings.

Time variability in Cenozoic reconstructions of mantle heat flow: plate tectonic cycles and implications for Earth's thermal evolution.

The thermal evolution of Earth is governed by the rate of secular cooling and the amount of radiogenic heating. If mantle heat sources are known, surface heat flow at different times may be used to deduce the efficiency of convective cooling and ultimately the temporal character of plate tectonics. We estimate global heat flow from 65 Ma to the present using seafloor age reconstructions and a modified half-space cooling model, and we find that heat flow has decreased by approximately 0.15% every million years during the Cenozoic. By examining geometric trends in plate reconstructions since 120 Ma, we show that the reduction in heat flow is due to a decrease in the area of ridge-proximal oceanic crust. Even accounting for uncertainties in plate reconstructions, the rate of heat flow decrease is an order of magnitude faster than estimates based on smooth, parameterized cooling models. This implies that heat flow experiences short-term fluctuations associated with plate tectonic cyclicity. Continental separation does not appear to directly control convective wavelengths, but rather indirectly affects how oceanic plate systems adjust to accommodate global heat transport. Given that today's heat flow may be unusually low, secular cooling rates estimated from present-day values will tend to underestimate the average cooling rate. Thus, a mechanism that causes less efficient tectonic heat transport at higher temperatures may be required to prevent an unreasonably hot mantle in the recent past.